Composition of matter



Patented Sept 18,: 1945 PATENT joma;

COMPOSITION OF MATTER Orland 'M. Reifi, Woodbury, N. J., assignor to Socony-Vacuum Oil Company, Incorporated, a corporation or New York No Drawing. Application January 1, 1943, Serial No. 471,023

20 Claims. (01. 260-399) This invention has to do with new chemical compounds or reaction products which may be generally designated as the sulfides, selenides and tellurides of the metal salts of alkyl-substituted l aromatic-organic carboxylic acids. Although the invention is broadly concerned with chemical compounds or compositions coming within the above-designated general classification, it contemplates as a preferred group coming within such general classification those compounds or condensation products which are soluble or miscible with mineral oil.

The present invention is based-upon the discovery that the oil-miscible sulfides, selenides and tellurides of metal salts of wax-substituted aromatic-organic carboxylic acids are of multifunctional activity when blended with viscous mineral oil fractions in that they effect improve: ment of several unrelated and related properties of the oil. For example, these preferred oilmiscible compounds or compositions which come Within the general field of invention contemplated herein -are effective when blended in a minor proportion with mineral oil fractions of the lubricant type, to depress the pour point, improve the viscosity index (V. I.) and inhibit oxidation of the oil. Through a proper choice of metal substituent (lead, copper, tin or zinc, for

example) the load-carrying capacity or "lubricity of the oil may also be improved.

The alkyl substituents on th aryl nucleus of the compounds or condensation products contemplated herein act to impart oil-miscibility to the product and for the preferred general, class of oil-miscible compounds these alkyl substituents should contain at least twenty carbon atoms. This preferred sub-group of compounds having the so-called "heavy alkyl groups of at least twenty carbon atoms (such as are derived, for example, from a Friedel-Crafts condensation with chlorinated par'aflin wax) act to improv the oil in the same respects-noted above, and in addition, they improve the viscosity index and pour point of the oil.

It is to be understood that the present inventionis not concerned with mineral o'l compositions, such compositions forming the subject matter of my copending application Serial No. 330,532, filed April 19, 1940, now Patent No. 2,319,189, issued May 11, 1943, of which the present application is a continuation-in-part and to which reference is made for further details in the composition of these compounds or reaction products.

It is also to be understood that the present invention is not confined to the oil-miscible or oil-soluble compounds and that the use of the preferred oil-miscible compounds is not confined to the improvement-of mineral oils, since this whole class of new materials is possessed of valuable properties irrespective of oil-miscibility. For example, the compounds or condensation products contemplated herein may be used as such as oil-soluble resins for use in paints and Y varnishes or as intermediates in the production of resins, resin-like materials, rubber substitutes,

etc. Certain of the compounds or compositions are possessed of valuable pharmaceutical, insecticidal, or similar properties, such, for example, as those derived from the presence of a particular metal or metal carboxylate group. Numerous other uses and applications of the compounds or compositions contemplated herein willbe readily apparent to those skilled in the art from the following description of their composition and. typical method of synthesis.

In the aforesaid copending application which is directed to mineral oil compositions havin incorporated therein the compounds or compositions of the present invention, and which is a continuation-in-part of my application Serial No.

300,010, filed October 18, 1939 (now Patent NO.

2,198,275), I have distinguished over the chemical compounds or compositions described in said patent. Briefly, the compounds or compositions of Patent No. 2,198,275 are alkyl-substituted aromatic-aliphatic carboxylic acid salts; whereas,

,the compounds or compositions of the present invention are sulfides, 'selenides or tellurides of alkyl-substituted aromatic-organic carboxylic acid salts wherein at least two of the alkylated aromatic-organic carboxyllc acid salt groups are interconnected by at least one atom of sulfur, selenium or tellurium. Thus, through the introduction of sulfur, for example, in the manner or manners to be hereinafter described, I obtain what may be broadly termed a sulfide of an alkylsubstituted aromatic-organic carboxylic acid in which the carboxyl hydrogen is substituted with its equivalent weight of metal.

'I'he'compounds of compositions contemplated by the present invention may be considered to be sulfides, selenides and tellurides of alkyl-substituted aromatic compounds in which at least one nuclear hydrogen of each aromatic nucleus is substituted with an oil-solubilizing alkyl group,

and in which at least one other nuclear hydrogen of each aromatic nucleus is substituted with an organic (preferably an aliphatic or cycloaliphatic) carboxylic acid salt radical wherein thecarboxyl ,tainin'g at least twenty carbon atoms is substituted for a nuclear hydrogen of each aromatic nucleus. Accordingly, compounds of this latter group which contain the metal-oxy group may be considered to be arylates or phenates for they contain the characterizing phenate group:

The compounds or compositions of the present invention may be further considered to be composed of at least two of the above-described alkylsubstituted aromatic compounds interconnected by at least one atom of an element selected from the group consisting of sulfur, selenium and tellurium and may be represented by the general formula:

MOOC.Z\ Z.COOM

in which Y represents an element selected from the group consisting of sulfur, selenium and tellurium, and nrepresents a whole number equal to at least 1 and preferably from 1 to 4. The group -Z-COOM represents what may be broadly termed an organic carboXylic acid salt group in which Z is preferably an aliphatic or cycloaliphatic hydrocarbon group, a carbon atom of which is directly attached to a carbon atom of the aromatic nucleus (benzene, thracene, phenanthrene. etc.); and COOM represents at least one carboxyl group attached to Z, the carboxyl hydrogen thereof being substituted with its equivalent weight of a metal M; R and R represent aliphatic hydrocarbon groups, at least one R and at least one R representing oil-solubilizing aliphatic radicals or groups conand a" rop resents an integer from 1 to 4.

It is to be understood, of course, that the aryl nuclei (disclosed in the formula above as substituted phenyl groups) may be either monocyclic or poly-cyclic, inwhich case a: may be greater than 4; also that it may carry other substituents, such as ester, keto, alkoxy, alkyl .Sul flde,.aryl sulfide, halogen, amino, hydroxy, metaloXy, etc, as more fully disclosed in applicat on Serial No. 330,532 of which this is, a continuationin-part. As indicated above; hydroxy and metaloXy radicals are preferred substituents of this group.

The organic carboXylate group, which constitutes one characterizing substituent in the aromatic nucleus of the compounds or compositions contemplated herein, is preferably either al phatic or cyclo-aliphatic and may be derived from the \corresponding organic acids of various molecular weights. In this regard. it is to be understood that the term alkyl" or aliphatic when used herein in connection with the organic carboxylate group, has reference to both aliphatic and cycle-aliphatic radicals, and that this alkyl car-- naphthalene, an-- boxylate group may contain at least one substituent selected fromthe group consisting of: alkyl, aralkyl, alkaryl, aryl, keto, ether, hydroxyl, halogen, nitro and amino radicals, etc., as disclosed in said .copending application Serial No. 330,532. Also, this alkyl carboxylate group may be monoor poly-basic; and in the event it is poly-basic, it is to be'understood that all of the carboxyl groups are substituted with metal.

In general, it appears that any metal may be employed as the metal M in compounds or condensation products of the aforesaid type to provide .valuable products. Particularly preferred metals are lead, copper, zinc, tin, barium, and

sodium. The metals contemplated herein, however, may be broadly classified as metals of groups I to VIII, inclusive, of the periodic system. These metals comprise the following: the alkali metals: lithium, sodium, potassium, rubidium and caesium; the alkaline earth group: beryllium, magnesium, calcium, strontium, and barium; the

,dymium, neodymium, Samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thalliumand lutecium.

Particularly preferred compounds or compositions contemplated herein are those in which the oil-solubilizing groups are aliphatic hydrocarbon radicals or groups characteristic of aliphatic hydrocarbons of high molecular weight and which may be termed heavy alkyl groups, For obtaining the preferred group of compounds or compositions which are miscible with mineral oil and whichpossess multifunctional oil-improving properties, I have found that this heavy alkyl" substituent in the sulfides (selem'des and tellurides) of the metal salts described above is preferably derived from a predominantly straightchain aliphatic hydrocarbon'of at least twenty carbon atoms such as characterize petroleum wax. As a matter of fact, paraffin wax is considered to be a preferred source of the "heavy alkyl substituent, and it is for that reason that the preferred compounds or compositions-described herein are referred to as wax-substituted. It is to be understood, however, that the term wax as used herein, is applied in a broad sense and is intended to includeany pure compound or mixture of compounds predominantly aliphatic in nature and containing at least twenty carbon atoms which is susceptible of attachment to an aromatic nucleus to provide a substituent which, in the proper proportions, will impart to the characterizing group the multifunctional oil-in roving properties referred to.

It will be understood that when a mixture of aliphatic hydrocarbon compounds such as cha acterize petroleum wax, for example, is used to provide the heavy alkyl substituent, the resulting composition will be an intimate mixture of sufa fides (selenides or tellurides) of alkyl-substituted As indicated above by the general formula, the

term sulfide as used herein is inclusive of the monosulfldes, disulfides, trisulfldes, tetrasulfldes, etc., that is, it includes both monosulfldes and polysulfides;. and it is also intended to includesuch polymers and related derivatives as may be formed by the procedures hereinafter described, which are provided to illustrate the synthesis of the compounds or reaction products contemplated herein. i

The sulfides or sulfur derivatives of alkylated aromatic-aliphatic acid salts are the preferred class of compounds or compositions contemplated herein, and for that reason, the invention will be specifically described in connection with the sulfur derivatives, although, as aforesaid, the corresponding selenides and tellurides are contemplated as coming within the scope of this invention.

The sulfides of-metal salts of alkyl-substituted aromatic-carboxylic acids can be prepared by the reaction of alkyl-substituted aromatic-carboxylic acids obtained as indicated in Patent No. 2,198,- 275, withsulfur or sulfur halides followed by substitution of the carboxyl hydrogen with metal.

With sulfur dichloride, for example, the mono- I sulfide (11:1 in general formula I) or polymer thereof is formed, and with sulfur monochloride the disulfide (11:2) or polymer thereof is formed. A mixture of sulfur monochloride and sulfur dichloride may be employed to obtain a corresponding mixture of condensation products. Sulfur condensation products or "sulfides of higher sulfur content can be formed by (a) reaction of alkyland mercaptosubstituted aromatic-carboxylic acids with sulfur monochloride or sulfur dichloride, and '(b) reaction of a compound of the general type hereinabove described havinga disulfide linkage, with sulfur or alkali polysulfide or alkyl tetrasuliide. p

The alkylated aromatic-aliphatic acids used in preparing the sulfur condensation products from which the corresponding metal carboxylates are formed, may be obtained in various ways. Details in desirable procedures for obtaining the preferred wax-substituted aromatic-aliphatic acids are described in the aforesaid Patent 2,198,275, where r such acids are intermediate products in the formation of the wax-substituted aromatic-aliphatic acid salts described and claimed therein.

The initial step in synthesizing the sulfides of alkylated aromatic-aliphatic acid salts, is to prepare the alkylated aromatic compound. A pre-= ferred procedure involves condensing a highmolecular weight aliphatic hydrocarbon material with the desired aromatic compound, which, as aforesaid, may carry other substituents, such as a hydroxy group, a metal-oxy group, or the like. The condensation may be affected by first halogenating the aliphatic material and condensing the same with aromatic material by means of a Friedel Crafts reaction, as described in detail in Patent 2,198,275, This alkylation may also be carriedout with unsaturated hydrocarbons or aliphatic valcohols, using sulfuric acid or anhydrous aluminum chloride as a catalyst. For obtaining the preferred multifunctional compounds carbon atoms, such as eicosylene, cerotene, melene, polymerized isobutylene, etc., and myricyi alcohol, ceryl alcohol, etc.

Examples of the aromatic compounds which may be used as starting materials for the alkylation or wax-condensation reaction for obtaining either a product in which the aromatic nucleus is otherwise unsubstituted or a product in which the aromatic nucleus carries a hydroxyl group are as follows: benzene, naphthalene-and anthracene (either substituted or unsubstituted); phenol, resorclnol, hydroquinone, catechol, cresol, hydroxy-diph'cnyl, benzyl phenol, alphaand betanaphthol and betal-methyl naphthol, anthranol, phenyi methyl naphthol, etc; and aryl others such as disphenyl ether and naphthyi ether. Mixed alkyl-aryl or aralkyl-aryl etherssuch as anisole, naphthyl methyl ether and benzyl phenyl ether can be used because the Friedei-Crafts re- 25 action with these ethers is accompanied by some re-arrangement, yielding free hydroxy groups. Preference, in general, as has been previously indicated, is to the monoand poly-cyclic aromatics (preferably naphthalene) and to the mono-hydroxy phenols otherwise unsubstituted, particular preference being given to phenol and alphaand beta naphthol.

The organic carboxylate substituent may be derived from any organic carboxylic acid, and preferably from any aliphatic or cyclo-aliphatic monoor poly-basic carboxylic acid, illustrative of which are acetic, butyric, valeric, heptylic, nonylic,rpalmitic and stearic acids, which typify /saturated acids, and must be used as the corre- 40 sponding halo-acid in which substitution takes place at the alpha carbonatoms of the aliphatic acid group. Other aliphatic acid substituents may be obtained by using unsaturated carboxylic acids of the oleic series, C2H2n-202, in which case substitution on the nucleus takes place at the I double bond of the unsaturated acid. Halogenated cyclo-aliphatic acids, such as chlornaphthenic acid may be used to obtain compounds in which the alkylated aromatic group carries a cyclo-aliphatic substituent. -The term "alkyl or fialiphatic" when used herein in connection with the aliphatic carboxylate substituent is intended as inclusive of both aliphatic and cycle-aliphaticacid groups or radicals.

Where it is desired to obtain a compound or condensation product in which the aryl nucleus contains another substituent in addition to or instead of residual hydrogen, it is pointed out that with the exception of substituents such as aral kyl, aryl, alkaryl, halogen, hydroxyl and aroxy, such substitueni', groups are introduced after alkylation and after introduction of the alkyl-carboxyl group. The usual methods for the introduction of these substituents into non-alkylated hydroxyaromatic and aromatic compounds may be employed in connection with the alirylated aromatic-alkyi acids and it is to be understood that the introduction of these substituents into the aromatic nucleus will in some cases be accompanied'by similar substitution in the heavy alkyl substituent and in the aliphatic acid group;

Me'thods'for the introduction of such substituents will be apparent from methods described in my aforesaid copending application Serial No. 330,-

ular weight compounds containing at least twenty a same designation As aforesaid, the preferred products contemplated herein are those having multifunctional properties wherein the alkyl substituent in the aryl nucleus contains at least" twenty carbon atoms. In this preferred class of compounds, special preference is products derived from allwl-substituted hydroxyaromatic compounds in which the alkyl substituent is derived from petroleum wax. The details in a typical procedure for synthesizing a so-called wax-substituted hydroxyaromatic compound, wax-phenol, are described in my prior application Serial No. 206,683 filed May 7, 1938 (now Patent No. 2,197,833, issued April 23, 1940). Briefly, this procedure involves reacting a chlorinated wax, such as chlorinated paraffin wax, with a phenol in the presence of a Friedel-Crafts catalyst at elevated temperature. The chlorine wax should have a chlorine content of from about 10 per cent to about 16 per cent, and the reaction mixture may contain about three atomic proportions of chlorine (in a chlorwax of 16 per cent chlorine content) to one molecular proportion of phenol. A wax-phenol" obtained from such areaction mixture maybe designated as wax-phenol (3-16). the type (A-B) will be used hereinafter in connection with the wax-substituted derivatives to designate: (A) the number of atomic propor tions of chlorine in the chlorinated wax reacted with one mol of hydroxyaromatic compound and (B) the chlorine content of. the chlorinated wax. In the above example A=3 and 3:16. The will also apply to the sulfides of metal salts of wax-substituted aromaticorganic carboxylic acids mate product derived from the wax-phenol.

Illustrative procedures which may be followed in preparing the sulfides of alkyl-substituted aromatlc-aliphatic acid salts are given in the following examples, wherein the alkylated phenol" is preferably a wax-substituted phenol of the type described directly above for obtaining the wax"-substituted derivatives which are especially preferred because of their multifunctional oilimproving properties.

EXAMPLE I PREPARATION OF STANNOUS CARBOXYLATE Wm- Parenthetical expressions ofgiven to the condensation proximately 9. A; blend in mineral '35 which constitute the ulti- The temperature of PHmvoL STEARIC Aorn Drsnnr'mn (a) Reaction mixture Parts by weight Wax-phenol stearic acid (3-14) 100' Mineral oil of 67 secs. S. U. V. 210, as diluent 300- Sulfur monochloride 5.05 Sodium (dissolved in butanol as sodium b'utylate) 3.46 Stannous chloride (anhydrous) 7.1

b) Reaction procedure Wax-phenol stearic acid (3-14) is prepared by condensingwax-phenol (3-14) with oleic acid,

according to the procedure described in Examples.

I(a)-(b)' of Patent 2,198,275. It is then diluted with mineral oil and converted to the sodium phenate-sodium carboxylate salt by reaction with sodium butylate by heating a mixture thereof at the refiux temperature- (about 225 F.) for one hour. The disodium salt is then further diluted with butanol until the mixture can be readily stirred at 100 F., and then S201: is added at this temperature at a rate sufficiently slow to avoid appreciable temperature rise by the heat of;

salts and the light diluent can be stannous chloride and the sodium salt to form the stannous carboxylate of wax phenol stearic acid disulfide. The alcohol is then distilled and the reaction produot'is filtered through Hi-Flo" to remove sodium chloride. The product is then steam treated at about 300 F. until all traces of alcohol solvent are removed. Upon cooling, vacuum is applied or a current of nitrogen is run through the mixture to remove water vapor and thereby obtain the finished product, which is apoil. By diluting the mixture sufficiently with Stoddards solvent or other appropriate light diluent, the mixture can be centrifuged to remove reaction removed by distillation in order to obtain the pure product per se.

EXAMPLE II SrArmoo's PrmN rn-SrAmvons WAx-PHENor. STEARIC Acm Dr- PREPARATION or CARBOXYLATE or SULFIDE (a) Reaction mixture A Parts by weight Wax-phenol stearic acid (3-14) Mineral oil of 67 secs. S. U. V, at 210 F.'as

(b) Reaction procedure The disodium salt of the wax-phenol stearic acid disulfide is formed by the procedure of Example I. In order to substitute both the phenolic and carboxyl hydrogens with tin, the stannous chloride in butanol solution is added, followed by addition of sodium butylate equivalent to the phenol content. One equivalent of stannous ibutylate and one equivalent of stannous chloride are then available for reaction with the sodium salt of the wax-phenol stearic 'acid-disulfide. the reaction mixture is then raised to reflux (about 225 F.) and said mixture is stirred for about one hour to complete the reaction. The alcohol is then distilled and the reaction mixture is filtered, steamed and purified as in Example I to obtain the pure product.

' EXAMPLE III PREPARATION or SI'ANNOUS CAnBoxYLAn or WAx- Mineral oil of 67 secs. S. U. V. at 210 F.

as di1'uent e 200 Sulfur monochloride 6.0

Sodium (dissolved in butanol as sodium butylate) I 2.0 8 5 Stannous 61115517; E555; III: I: I

The stannous multifunctional improving (1:) Reaction procedure Wax-phenoxy phenyl stearic acid (3-16) is prepared by condensing wax-phenyI ether (3-16) with oleic acid, according to the procedureoutlined in Example III(a) oi Patent 2,198,275. It is then diluted with mineral oil and converted to the sodium salt by reaction with sodium butylate by heating a mixture thereof at the reflux temperature of butanol for one hour. Sulfur monochloride is added at about 100 F. at a rate regulated to prevent appreciable temperature rise by the resulting heat of reaction; it is preferable for obtaining light colored products that the temperature be not too high at this stage of the preparation. The mixture is stirred at this temperature for one hour to complete the suliurization. In the reaction with sulfur monochloride, the sodium salt is neutralized by reaction with the hydrochloric acid iormed, resulting in the formation of the wax-phenoxy phenyl stearic acid disulflde as the reaction product. Stannous chloride is added to the free acid to form the corresponding stannous salt, followed by addition of an equivalent amount of sodium butylate and heating at the reflux temperature for about one hour to complete the reaction. In this reaction, stannous butylate is termed by reaction of stannous chloride with sodium butylate, and in turn, is reacted with the carboxyl group to form the stannous carhoxylate derivative. The alcohol is then distilled ed and the reaction product is filtered to -remove sodium chloride. The product thus obtained is steam-treated at about 300 F. to remove any traces oi solvent. Upon. cooling, vacuum. is 'applied or a current of nitrogen is run through the mixture to remove water vapor to give the had product. The pure product per so may be obtained by following the purification procedure indicated in Example I.

sulfides of wax-substituted aromatic-aliphatic acid salts, which represent a preferred group or compounds or compositions, of the general character described above which are derived from wax-phenol, may be broadly classified as sulfides of wax phenyl aliphatic acid salts. Corresponding sulfides can be prepared from wax-substituted aromatic compounds other than phenol, either monoor poly cyclic and substituted or unsubstituted, an example of which is wax-naphthol (34s). as aforesaid, high molecular weight all- Ichatic compounds or materials other than petroleum wax may be used as the source oithe heavy allsyl (was) substituent, and it is also emphasized that the invention is not limited to products obtained irom stearic acid as a source of the aliphatic acid substituent but any halogenated aliphatic or cyclo aiiphatic acid, including the alkali salt thereof, can be used to obtain various aliphatic and, cycle-aliphatic radicals or groups in the aliphatic or cycle-aliphatic acid salt substituent.

sulfides oi wax-aryl aliphatic salts or the type described above are highly viscous rubber-like products, which with the phenolic ratio properly controlled are readily soluble in mineral oils.

Their 0010;- is such that they can be readily blended with light colored mineral oil fractions without substantial darkening of the oil'fraction, which makes them particularly desirable for use inthisconnection.

Although products f the oil-miscible type are designated herein as preferred, because of their properties in mineral oil blends, it is again emphasized that the-invention is not limited to sulfides (selenides or tel lurides) of metal salts of wax-aryl aliphatic acids in which the phenolic ratio is adjusted for oil solubility, but that it is inclusive of this entire field of products irrespective of oil-solubility.

Listed below are several typical compounds of the type contemplated herein. The procedures for preparing these compounds or reaction products will be apparent-to those skilled in the art from the foregoing examples of representative procedures.

Stannous carboxylate of wax-phenol stearic acid disulfide Stannous phenate-stannous carboxylate of wax-phenol stearic acid disulfide Stannous carboxylate of wax-phenoxy phenyl stearic acid disulfide Stannous carboxylate of waxnaphthyl stearic acid monosulflde Barium carboxylate of wax-phenyl palmitic acid disulfide Barium phenate-barium carboxylate of waxphenol palmitic acid ,disulfide.

Zinc carboxylate of wax-phenol stearic acid tetrasulfide Zinc'naphthate-zinc carboxylate of wax-naph thol stearic acid disulfide Plumbous carboxylatepf wax-phenol nonylic acid trisulfide Plumbous phenate-plumbous carboxylate oi wax-phenol stearic acid monosulfide.

modifications as fairly come within the spirit of l the appended claims.

Iclaim:

1. A new composition of matter consisting of the condensation product characterized by at least two aromatic nuclei interconnected by at least one atom of an element selected from the group consisting of sulfur, selenium and tellurium, each or said aromatic nuclei having attached thereto an organic aliphatic carboxylic acid group, a carbon of which is directly atcachedv to a. carbon atom of the aromatic nucleus, the carboxyl hydrogens of said organic aliphatic carboxylic acid groups being substituted with metal, and each of said aromatic nuclei being substituted-with at least one alkyl group.

2. A new composition of matter consisting of the condensation product characterized by at least two aromatic nucleiinterconnected by at least one atom of an element selected from the group consisting oi sulfur,v selenium and'telluat least twenty carbon atoms.

3. A new composition or matter consisting of the condensation product characterized by at least two aromatic nuclei interconnected by at least one atom of sulfur, eacli'oi said aromatic nuclei having attached thereto an organic aliphatic carboxylic acid group. a carbon or which is directly attached to a carbon atom of the aromatic nucleus, the carboxyl hydrogens of said organic aliphatic carboxylic acid groups being substituted each ofsaid aromatic nuclei having atwith metal, and each of said aromatic nuclei being substituted with at least one wax group,

aromatic nuclei having atsaid aromatic nuclei having attached thereto an organic aliphatic carboxylic acid group, a carbon of which is directly attached to a carbon atom of the aromatic nucleus, the carboxyl hydrogens of said organic aliphatic carboxylic acid groups being substituted with metal, each of said aromatic nuclei being substituted with a hydroxy group, and each of said aromatic nuclei being substituted with at least one wax group.

6. A new composition of matter consisting of a metalorganic compound having the general formula:

Mooc-z Z-COOM in which Y is an element selected from the group consisting of sulfur, selenium and tellurium; n,

is a whole number'from 1 to 4; -Z -COOM represents an organic carboxylic acid saltv group in which Z represents a radical selected from the group consisting of alkyl. and cycloalkyl radicals, a carbon atom of which carbon atom of a benzene nucleus; -COOM represents at least one carboxyl group attached to the radical Z, the carboxyl hydrogen thereof being substituted by a metal M; R and R represent alkyl groups having at least twenty carbon atoms; and a: is a whole number from 1 to 4.

7. A newv composition of matter consisting of a metalorga'nic compound having the general formula: v

MOOC-Z Z-COOM in which Y is an element selected from consisting of sulfur, selenium and the group tellurium; n

a is a whole number from 1 to 4; -Z-COOM repreated petroleum wax; and an is a whole number 6 wherein the metal is selected from the group organic aliphatic carboxylic is directely attached to a consisting oflead, copper, zinc, tin, barium and sodium.

9. A composition of matter 6 in which the metal is tin.

10; A composition of matter as defined in claim 7 wherein the metal is selected from the group consisting of lead, copper, zinc, tin, barium and sodium. 7

11., A composition of matter as defined in claim 7 in which" the metal is tin.

12. A new composition of matter consisting of stannous carboxylate of wax-phenol stearic acid disulfide.

13. A new composition of matter consisting of stannous phenate-stannous carboxylate of waxphenol stearic acid disulfide.

14. A new composition of matter consisting of as defined in claim stannous carboxylate of wax-phenoxy phenyl stearic acid disulfide. 15. A new composition of matter consisting of essentially aliphatic hydrocarbon groups having a composition corresponding substantially to the different aliphatic hydrocarbons contained m form the '18. The

corresponding sulfide methodof preparing a sulfide of a of a. wax-substituted aromatic-ali- T of a Friedel-Crafts catalyst to form a wax-substituted aromatic hydrocarbon product; then condensing said wax-substituted ing the carboxyl hydrogen of said reacting the alkali metal alkali metal Salt thus with a sulfur halide to form the said salt; and by metathesis substituting the metal in the sulfide of said formed, with another salt thus formed corresponding sulfide of metal.

19. The method of preparing a sulfide of a metal carboxylate salt of a wax-substituted hydroxyaromatic-aliphatic carboxylic acid which comprises: first condensing a. hydroxyaromatic hydrocarbon compound with a halogenated parafiin wax in the presence of a Friedel-Crafts catalyst to form a wax-substituted hydroxyaromatic hydrocarbon product; then condensing said waxsubstituted aromatic hydrocarbon product with a halogenated aliphatic carboxylic acid toobtain a wax-substituted hydroxyaromatic-aliphatic carboxylic acid; then-substituting the carboxyl and hydroxyl hydrogens of said hydroxyaromatic-aliphatic carboxylic acid with alkali meta1; reacting the alkali arylate-alkali carboxylate salt thus formed with a sulfur halide to form the corresponding sulfide of the wax-substituted hydroxyaromatic-aliphatic carboiwlate salt in which only the carboxyl hydrogen is substituted with alkali metal; and by metathesis, substitutgens with alkali product obtained -ylic acid which comprises:

droxyaromatic-aliphatic carboxylic acid;- then substituting the carboxyl and hydroxyl hydrometal; reacting the alkali andate-alkali carboxylate salt thus formed with a sulfur halide to form the corresponding sulfide of the wax-substituted hydrcbty-aromatic-ailphatic'carboxylate salt in which only the carboxy! hydrogen is substituted with alkali metal; and by metathesis, substituting another metal for the alkali metal and the hydroxyl hydrogen in the product obtained in the preceding step.

, ORLAND M. REEF.- 

